CN113351026A - Preparation method of polyamide composite membrane with high controllability - Google Patents
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- 239000012528 membrane Substances 0.000 title claims abstract description 126
- 239000002131 composite material Substances 0.000 title claims abstract description 98
- 239000004952 Polyamide Substances 0.000 title claims abstract description 65
- 229920002647 polyamide Polymers 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 27
- 150000001412 amines Chemical class 0.000 claims abstract description 24
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 18
- LSICDRUYCNGRIF-UHFFFAOYSA-N n,n-dimethylheptan-1-amine Chemical compound CCCCCCCN(C)C LSICDRUYCNGRIF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001263 acyl chlorides Chemical class 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 10
- 229920000768 polyamine Polymers 0.000 claims description 10
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical group NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 9
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical group ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 5
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 3
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 3
- RUOKPLVTMFHRJE-UHFFFAOYSA-N benzene-1,2,3-triamine Chemical compound NC1=CC=CC(N)=C1N RUOKPLVTMFHRJE-UHFFFAOYSA-N 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 24
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- 229920002492 poly(sulfone) Polymers 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000001223 reverse osmosis Methods 0.000 description 6
- 238000007112 amidation reaction Methods 0.000 description 5
- 239000004760 aramid Substances 0.000 description 5
- 229920003235 aromatic polyamide Polymers 0.000 description 5
- 238000012696 Interfacial polycondensation Methods 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- -1 trimesoyl chloride amine Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 239000012527 feed solution Substances 0.000 description 2
- 238000009292 forward osmosis Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960000074 biopharmaceutical Drugs 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a preparation method of a polyamide composite membrane with high controllability. The organic amine is one or more of N, N-dimethyl heptanamine, N-dimethyl nonyl amine, N-dimethyl N-octyl amine, N-dimethyl decyl amine, N-dimethyl dodecyl amine, etc., the mass concentration is 0.01-2.0%, and the coating amount is 30-300ml/m2. The invention has the advantages that: (1) the density and the surface charge density of the polyamide composite membrane separation layer can be effectively and accurately regulated and controlled; (2) the preparation method is simple to operateThe method has wide application range and easy scale production, and can effectively improve the controllability and the performance consistency of the polyamide composite membrane prepared by interfacial polymerization.
Description
Technical Field
The invention relates to a preparation method of a polyamide composite membrane, in particular to a preparation method of an interfacial polymerization polyamide composite membrane with high controllability, and belongs to the technical field of preparation of separation membranes.
Background
The membrane separation technology has the advantages of high efficiency, low energy consumption, easy operation and the like, is widely applied to the fields of drinking water purification, wastewater treatment, bio-pharmaceuticals, petrochemical industry and the like, and is an important support technology for solving the problem of water resource shortage and realizing the resource utilization of wastewater at present. Reverse osmosis, nanofiltration, forward osmosis and the like are used as membrane processes for molecular level separation, and are widely applied to the fields of water desalination and purification, material separation and concentration, wastewater recycling and the like. The core of the membrane separation technology is a high-performance separation membrane, and currently used membrane materials mainly comprise cellulose acetate, aromatic polyamide, sulfonated polysulfone and the like. The polyamide composite membrane prepared by interfacial polymerization of polyamine and polybasic acyl chloride has excellent water permeability and selective separation performance, and is a mainstream membrane product in the technical fields of membrane separation such as reverse osmosis, forward osmosis, nanofiltration and the like at present.
US Patent 4,277,344 uses an interfacial polycondensation process to prepare polyamide reverse osmosis composite membranes. The membrane is prepared by immersing a polysulfone porous support membrane into an aqueous solution containing m-phenylenediamine for a certain time, taking out and squeezing, covering a trimesoyl chloride solution on the surface of the support membrane, reacting for a period of time, performing heat treatment at a certain temperature, and finally rinsing and post-treating to obtain a final product. US Patent 4,761,234 adopts an interfacial polycondensation process, an aromatic polyamide film is compounded on a porous polysulfone support membrane through interfacial polymerization between pyromellitic triamine and isophthaloyl dichloride, and a reverse osmosis composite membrane is prepared through high-temperature heat treatment and water rinsing treatment, wherein the membrane desalination rate is more than 99.0%. The method is characterized in that a mixture of trimesoyl chloride and isophthaloyl chloride is used as polybasic acyl chloride to react with m-phenylenediamine on a polysulfone porous support membrane to form an aromatic polyamide desalting layer by adopting an interfacial polymerization process, and a polyamide composite membrane with negatively charged surface is obtained by high-temperature heat treatment and water rinsing treatment. U.S. Pat. No. 5,641,09 employs an interfacial polycondensation process, and a layer of aromatic polyamide film is reacted and compounded on a porous polysulfone support membrane through interfacial polymerization between an isopropanol-containing m-phenylenediamine aqueous solution and trimesoyl chloride amine, and the reverse osmosis composite membrane with high flux and negative surface charge is prepared through high-temperature heat treatment and water rinsing treatment. US Patent 6,162,358 adopts an interfacial polycondensation process, reacts and compounds a layer of aromatic polyamide film on a porous polysulfone support membrane through interfacial polymerization between metaphenylene diamine aqueous solution containing monophenol and trimesoyl chloride, and prepares a high-flux reverse osmosis composite membrane through high-temperature heat treatment and water rinsing treatment.
In summary, the interfacial polymerization process based on the polyamine and the polyacyl chloride functional monomer is the mainstream process for preparing the polyamide composite membrane at present. The interfacial polymerization for preparing polyamide composite membranes generally comprises the following steps:
(1) quantitatively coating an aqueous phase solution containing polyamine on a porous support membrane;
(2) quantitatively coating an organic phase solution containing polybasic acyl chloride on the surface of a porous membrane containing polybasic amine, and carrying out interfacial polymerization reaction to obtain a nascent state polyamide composite membrane;
(3) and carrying out heat treatment and water rinsing treatment on the nascent state composite membrane.
The heat treatment process aims to carry out high-temperature treatment on the nascent state composite membrane generated by interface polymerization, and further improves the crosslinking degree and the density of the polyamide separation layer through amidation reaction between unreacted acyl chloride and amino groups at high temperature; and in the water rinsing treatment process, the last residual acyl chloride group is hydrolyzed to generate carboxyl, so that negative electricity is given to the surface of the composite membrane. However, the above interfacial polymerization for preparing a polyamide composite film has the following problems: firstly, the amount of acyl chloride and amino groups participating in high-temperature amidation reaction can not be quantitatively controlled in the heat treatment process of the nascent state composite membrane, so that the density consistency of a separation layer is poor; on the other hand, the amount of the final residual acyl chloride group on the surface of the composite membrane after the heat treatment cannot be controlled, so that the consistency of the negative charge density on the surface of the polyamide composite membrane after the water rinsing treatment is poor. Because the selectivity and separation performance of the polyamide composite membrane has larger correlation with the density and surface negative charge density of the separation layer, the controllability of the separation performance of the polyamide composite membrane prepared by the prior art is poorer, namely the controllability of the polyamide composite membrane prepared by the prior general interfacial polymerization process is poorer.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a polyamide composite membrane with high controllability, which can effectively improve the controllability and the membrane performance consistency of the polyamide composite membrane prepared by interfacial polymerization.
The technical problem to be solved by the invention is how to control the amount of unreacted acyl chloride groups on the surface of the nascent polyamide composite membrane to perform amidation reaction and how to control the amount of residual acyl chloride converted into carboxyl in the rinsing treatment process in the high-temperature heat treatment process, so as to ensure the consistency of the density of a separation layer of the polyamide composite membrane and the density of negative charges on the surface. On the basis of a conventional interfacial polymerization process, an organic solution containing organic alkali is coated on the surface of the nascent state polyamide composite membrane before high-temperature heat treatment, acyl chloride groups on the surface of the nascent state composite membrane are quantitatively converted into intermediate products, the amount of the acyl chloride groups participating in amidation reaction in the heat treatment process is further controlled, and the intermediate products can be converted into carboxyl groups after being rinsed, so that the accurate regulation and control of the crosslinking degree (density) and the surface negative charge density of a separation layer of the polyamide composite membrane are realized, and the preparation controllability and the performance consistency of the interfacial polymerization polyamide composite membrane are improved.
The invention is realized by the following technical scheme:
a preparation method of a polyamide composite membrane with high controllability is characterized by comprising the following preparation steps:
(1) quantitatively coating an aqueous phase solution containing polyamine on a porous support membrane;
(2) quantitatively coating an organic phase solution containing polybasic acyl chloride on the surface of a porous membrane containing polybasic amine, and carrying out interfacial polymerization reaction to obtain a nascent state polyamide composite membrane;
(3) carrying out surface coating treatment on the nascent polyamide composite membrane by using an organic amine-containing solution prepared by an organic solvent;
in the prior preparation process of the composite membrane, the steps of heat treatment, water rinsing and the like are directly carried out on the composite membrane after interfacial polymerization reaction, so that the final result of the composite membrane is unstable, the requirement of uniformity in each production process cannot be met, and the quality of a membrane product is uncontrollable.
Preferably, the organic solvent in step (3) is the same organic solvent as the organic phase solution prepared in step (2).
(4) And carrying out heat treatment and water rinsing treatment on the polyamide composite membrane.
Preferably, in the preparation method of the polyamide composite membrane with high controllability, the polyamine is m-phenylenediamine, methyl m-phenylenediamine, piperazine, trimesamine or a mixture of the m-phenylenediamine and the m-phenylenediamine.
Preferably, in the method for preparing the polyamide composite membrane with high controllability, the poly-acyl chloride is trimesoyl chloride, isophthaloyl chloride, terephthaloyl chloride or a mixture thereof.
Preferably, in the method for preparing the polyamide composite membrane with high controllability, the organic amine is N, N-dimethyl heptanamine, N-dimethyl nonyl amine, N-dimethyl N-octyl amine, N-dimethyl decyl amine, N-dimethyl dodecyl amine or a mixture thereof.
Preferably, in the preparation method of the polyamide composite membrane with high controllability, the mass concentration of the organic amine is 0.01-2.0%, and the coating amount is 30-100ml/m2。
The polyamide composite membrane is a flat membrane, or a hollow fiber membrane, or a tubular membrane.
Compared with the prior art, the invention has the beneficial effects that: according to the preparation method, through the reaction of organic amine and acyl chloride on the surface of the nascent state polyamide composite membrane, acyl chloride groups on the surface of the nascent state composite membrane are quantitatively converted into intermediate products, the amount of acyl chloride groups participating in amidation reaction in the heat treatment process is further controlled, and the intermediate products can be converted into carboxyl groups through rinsing, so that the accurate regulation and control of the crosslinking degree (density) and surface negative charge density of a separation layer of the polyamide composite membrane are realized, the preparation controllability and performance consistency of the interfacial polymerization polyamide composite membrane are improved, and the preparation of the high-controllability polyamide composite membrane is realized.
Detailed Description
The following is a detailed description of the practice of the invention;
the following examples provide methods and effects for preparing a polyamide composite membrane with high controllability. However, these examples are provided only for illustration and not for limiting the invention.
Preparing a polyamide composite film: preparing a polyamide composite membrane by the following steps:
firstly, a polysulfone porous support membrane with the aperture of about 30nm is immersed into an aqueous solution containing 3.0 wt% of triethylamine, polyamine, 0.2 wt% of sodium dodecyl sulfate and 5.0 wt% of camphorsulfonic acid for 3.0 minutes, and the aqueous solution is taken out, drained and dried by nitrogen. Wherein the polyamine is metaphenylene diamine, methyl metaphenylene diamine, pyromellitic triamine or their mixture, and the content is 3.0 wt%.
Contacting the support film containing polyamine with n-heptane solution containing polybasic acyl chloride on one side to perform interfacial polymerization reaction for 60 s to obtain nascent state polyamide composite film. Wherein the polybasic acyl chloride is trimesoyl chloride, or isophthaloyl chloride, or terephthaloyl chloride, or the mixture thereof, and the content is 0.15 wt%.
Thirdly, coating the surface of the nascent polyamide composite membrane by using an organic amine-containing solution prepared by using an organic solvent used by the organic phase solution; wherein the organic amine is N, N-dimethyl heptanamine, N-dimethyl nonyl amine, N-dimethyl N-octyl amine, N-dimethyl decyl amine, N-dimethyl dodecyl amine, or their mixture, the mass concentration is 0.01-2.0%, and the coating amount is 30-300ml/m2。
Fourthly, the polyamide composite membrane is thermally treated for 10 minutes at the temperature of 80 to 90 ℃, and then rinsed for 60 minutes by pure water.
And (3) evaluating the separation performance of the polyamide composite membrane: the solute removal rate and the water flux are two important parameters for evaluating the separation performance of the polyamide composite membrane. The polyamide composite membrane was evaluated for sodium chloride (solute) removal rate and water flux by cross-flow permeation test.
The solute removal rate (R) is defined as: feed solution solute concentration (C) under certain operating conditionsf) With the concentration of solute (C) in the permeatep) The difference is divided by the feed solution solute concentration. The specific calculation formula is as follows:
water flux (F) is defined as: under certain operating conditions, the volume (V) of water per unit membrane area (A) permeated per unit time (t) is expressed in l/m2H. The specific calculation formula is as follows:
the operation conditions adopted for measuring the separation performance of the composite membrane are as follows: the feed liquid is 1000mg/l sodium chloride aqueous solution, the operating pressure is 1.0MPa, the operating temperature is 25 ℃, and the pH of the solution is 6.8.
As a result:
comparative examples 1 to 6:
the polyamide composite membrane is prepared by adopting a conventional interfacial polymerization process, and the surface of the nascent state composite membrane is not coated with an organic solution containing organic amine. The batch separation performance of the prepared polyamide composite membrane is shown in table 1.
Table 1: comparative examples 1 to 6
The above examples show that: the polyamide composite membrane is prepared by adopting a conventional interfacial polymerization process, organic solution containing organic amine is not coated on the surface of the nascent state composite membrane for treatment, the performance difference of the composite membrane among different batches is large, and the preparation controllability of the composite membrane is poor.
Examples 7 to 12:
the polyamide composite membrane is prepared by adopting the prior art, and before the heat treatment of the nascent state composite membrane, the nascent state composite membrane is subjected to surface coating treatment by using an organic solvent solution containing 0.02 percent of N, N-dimethyl heptanamine, wherein the coating amount is 60ml/m2. Batch separability of the obtained polyamide composite membraneCan be as shown in table 2.
Table 2: examples 7 to 12
The above examples show that: organic solution containing organic amine is coated on the surface of the nascent state composite membrane for treatment, so that the performance difference of the composite membrane among different batches is small, and the controllability and the consistency of the performance of the composite membrane are good.
Examples 13 to 18:
a polyamide composite membrane was prepared in the same preparation method as in example 7, except that the kind of the organic amine was different. The batch separation performance of the prepared polyamide composite membrane is shown in table 3.
Table 3: examples 13 to 18
The above examples show that: the surface coating treatment is carried out on the nascent state composite membrane by adopting organic solutions of different organic amines, the performance difference of the composite membrane among different batches is small, and the controllability of the preparation of the composite membrane and the consistency of the membrane performance can be improved.
Examples 19 to 23:
a polyamide composite membrane was prepared in the same preparation method as in example 8, except that the organic amine concentration was varied. The batch separation performance of the prepared polyamide composite membrane is shown in table 4.
Table 4: examples 19 to 23
The above examples show that: the surface coating treatment is carried out on the nascent state composite membrane by adopting organic amine solutions with different concentrations, the performance difference of the composite membrane among different batches is small, the controllability of the preparation of the composite membrane and the consistency of the membrane performance can be improved, and the correlation between the performance of the composite membrane and the concentration of the organic amine is good.
Examples 24 to 28:
a polyamide composite membrane was prepared in the same preparation method as in example 12, except that the coating amount of the organic amine solution was different. The batch separation performance of the prepared polyamide composite membrane is shown in table 5.
Table 5: examples 24 to 28
The above examples show that: different amounts of organic amine solutions are coated on the surface of the nascent state composite membrane, the performance difference of the composite membrane among different batches is small, the controllability of the preparation of the composite membrane and the consistency of the membrane performance can be improved, and the performance of the composite membrane is well related to the amount of the coated organic amine solution.
Claims (6)
1. A preparation method of a polyamide composite membrane with high controllability is characterized by comprising the following preparation steps:
(1) quantitatively coating an aqueous phase solution containing polyamine on a porous support membrane;
(2) quantitatively coating an organic phase solution containing polybasic acyl chloride on the surface of a porous membrane containing polybasic amine, and carrying out interfacial polymerization reaction to obtain a nascent state polyamide composite membrane;
(3) carrying out surface coating treatment on the nascent polyamide composite membrane by using an organic amine-containing solution prepared by an organic solvent;
(4) and carrying out heat treatment and water rinsing treatment on the polyamide composite membrane.
2. The method of claim 1, wherein the polyamine is m-phenylenediamine, m-phenylenediamine-methyl, piperazine, or benzenetriamine, or a mixture thereof.
3. The method according to claim 1, wherein the poly-acyl chloride is trimesoyl chloride, isophthaloyl chloride, or terephthaloyl chloride, or a mixture thereof.
4. The method as claimed in claim 1, wherein the organic amine is N, N-dimethylheptanamine, N-dimethylnonamine, N-dimethyl-N-octylamine, N-dimethyldecylamine, N-dimethyldodecylamine, or a mixture thereof.
5. The preparation method of the polyamide composite membrane with high controllability according to claim 1, wherein the mass concentration of the organic amine is 0.01-2.0%, and the coating amount is 30-100ml/m 2.
6. The method for preparing a polyamide composite membrane with high controllability according to claim 1, wherein the organic solvent in the step (3) is the same organic solvent as the organic phase solution prepared in the step (2).
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| CN114870645A (en) * | 2022-03-17 | 2022-08-09 | 浙江理工大学 | Method for improving flux of composite reverse osmosis membrane prepared by interfacial polymerization method |
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| CN106563360A (en) * | 2016-11-02 | 2017-04-19 | 浙江理工大学 | Preparation method of low-charge reverse osmosis composite film |
| CN110038446A (en) * | 2019-05-31 | 2019-07-23 | 自然资源部天津海水淡化与综合利用研究所 | A kind of antipollution aromatic polyamide composite reverse osmosis membrane and preparation method thereof |
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| CN114870645A (en) * | 2022-03-17 | 2022-08-09 | 浙江理工大学 | Method for improving flux of composite reverse osmosis membrane prepared by interfacial polymerization method |
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